Morphology of elastic poly(L-lactide-co-ε-caprolactone) copolymers and in vitro and in vivo degradation behavior of their scaffolds

Very elastic PLCL [poly(L-lactide-co-ε-caprolactone), 50:50] copolymers were synthesized and extruded into porous tubular scaffolds (pore size 150 ± 50 μm, porosity 90%) for the application to tissue engineering. The copolymers were basically random and amorphous. However, two T_g's (glass transition temperatures) were observed in dynamic mechanical thermal analysis and also in differential scanning calorimetry thermograms. Furthermore, microdomains (about 17 nm in size) were indicated on the small-angle X-ray scattering profile and finally confirmed by transmission electron microscopy. Therefore, the PLCL copolymer was probably composed of a soft matrix of mainly ε-caprolactone moieties and hard domains containing more L-lactide units to exhibit a rubberlike elasticity in virtue of the physically cross-linked structure. The smooth muscle cells seeded scaffolds were implanted into nude mice subcutaneously for up to 15 weeks to monitor the in vivo degradation. In addition, they were degraded in vitro in phosphate buffer solution (pH 7.4) for up to 1 year to compare the results each other. All the scaffolds degraded slowly in vivo and in vitro even in the form of a highly porous thin membrane. However, the degradation rate was somewhat faster for in vivo than for in vitro. This should be explained by enzymes that might have played a certain role in the degradation in the body. In addition, the ε-caprolactone moieties degraded faster than the L-lactide units did in these PLCL scaffolds, although their hydrophilicities are in the opposite order. This behavior appeared more prominently in the in vivo case. This should result from that the amorphous regions composed of mainly ε -caprolactone units might have been first attacked by water because water can penetrate into the amorphous regions easier than the hard domains containing more L-lactides.